Acrylonitrile polymers with anti-static properties

ABSTRACT

The invention relates to acrylonitrile polymers or copolymers containing as an anti-static agent from 1 to 20 percent by weight based on the mixture as a whole of polyalkylene oxide derivatives with terminal sulphonate groups attached through alkylphenyl ether groups.

United States Patent [1 1 Radlmann et al.

[451 Apr. 1, 1975 ACRYLONITRILE POLYMERS WITI-I ANTI-STATIC PROPERTIES[75] Inventors: Eduard Radlmann; Gunther Nischk,

both of Dormagen, Germany [73] Assignee: Bayer Aktiengesellschat't,

Leverkusen, Germany 22 Filed: Apr. 13, 1973 21 Appl. No.: 350,959

[30] Foreign Application Priority Data Apr. 14, 1972 Germany 22l7974[58] Field of Search.,... 260/85.5 R, 85.5 D, 88.7 R, 260/88.7 D, DIG.l5, DIG. l6, DIG. 19, 45.85 N, 45.85 P, 45.9 P, 45.95 R, 45.95 C,

[56] References Cited UNITED STATES PATENTS 3,737,420 6/1973 Brokmeieret al...... 260/85.5 R V 3,743,685 7/1973 Grosjean et al 260/DIG. 15

Primary Examiner,-I larry Wong, Jr. Attorney, Agent, or FirmPlumley &Tyner [5 7] ABSTRACT I The invention relates to acrylonitrile polymersor copolymers containing as an anti-static agent from 1 to 20 percent byweight based on the mixture as a whole of polyalkylene oxide derivativeswith terminal sulphonate groups attached through alkylphenyl ethergroups.

6 Claims, No Drawings ACRYLONITRILE POLYMERS WITH ANTI-STATIC PROPERTIESThis invention relates to acrylonitrile polymers with reduced surfaceresistance.

Since the surface resistance of shaped articles, especially fibres, ofpolyacrylonitrile or acrylonitrile copolymers is greater than 10 Ohms,the potential commercial applications of materials of this kind arelimited on account of the extremely troublesome electrical charge.

There is an extensive literature on tests to provide acrylonitrile-basedpolymers with an anti-static finish, such as applying anti-staticallyactive substances to the surface of the shaped articles, introducingsuitable substrates into the melt or solution of the polymers, followedby forrning, or copolymerising the acrylonitrile with anti-staticallyactive comonomers, in such a way that their surface resistance falls tovalues below 10 Ohms.

A permanent anti-static effect can seldom be obtained by applyingsuitable compounds because shaped articles are generally exposed tomechanical or solvolytic influences which remove the surface coating.Acrylonitrile copolymers with comonomers which'reduce surface resistanceshould have the most favourable antistatic effect because the activeconstituents are firmly anchored in the polymer chain. In this case,however, considerable difficulties are encountered during polymerisationin the case of conventional systems.

No problems are involved in adding anti-statically active substratesbefore the forming stage. The requirements which substances of this kindhave to satisfy include high compatibility with the polymer, resistanceto temperature stressing, resistance to evaporation, hydrolyticinfluences or washing out with water or organic solvents.

' Conventional anit-static additives are based on compounds from suchclasses as ureas, dithiocarbonates, phosphoric acid amides,aminocarboxylic acid amides, polyethylene oxides, and oxalkylatedaliphatic or aromatic alcohols with terminal sulphonate groups which areintroduced through aliphatic ether groups with sultones or w-halogenalkane sulphonates.

It has now been found that polyalkylene oxide derivatives with terminalsulphonate groups attached through alkylphenyl ether groups showoutstanding anti-static activity as additives to acrylonitrile polymers.The reduction which these additives produce in electrical surfaceresistance is also obtained in some other synthetic polymers.

According to the invention there is provided a compound corresponding tothe general formula (I) m is an integer of from 1 to 150;

M represents a member selected from the group consisting of an alkalimetal, alkaline earth metal, an ammonium radical and an alkylammoniumradical;

R represents hydrogen or a methyl radical;

5 R represents a member selected from the group consisting of, hydrogen,a lower alkyl radical with from 1 to 6 carbon atoms, fluorine, chlorine,bromine and iodine;

R represents a member selected from the group con- 10 sisting ofhydrogen, Nl-l NO CN, CF

Cl and R R I l SO O-CH-CH A in which R, M and m are defined above; and Arepresents a radical selected from the group consisting of O $3 R 0-, R-N, R -N B -c-0-, (111) (IV). (v) -(v1) 1 2 (VII M0 R' R 40 l l R0-CH-CH 0-R ,-O

R M0 5 n 0 o l H ll R CH-CH U-C-R -CO 2 1 I R in which R, R R M and mare as defined above, R represents a radical selected from the groupconsisting of an alkyl radical with from 1 to 30 carbon atoms, an aryl,alkylaryl and arylalkyl radical, and R represents a number selected froman alkylene radical with from 1 to 30 carbon atoms and an aryleneradical; and n represents the number 1 or 2.

so 14 1} 3 e A H-GH- 2 (I) in which A, R, R R M, m and n are as definedabove, and spinning the solution or melt.

The novel anti-static agents added in accordance with the invention areprepared by converting polyether diols of ethylene oxide or propyleneoxide or oxalkylation products, preferably with ethylene oxide,propylene oxide or mixtures of the two reacted aliphatic or aromaticalcohols and diols, primary or secondary aliphatic or aromatic amines,monoor dicarboxylic acids corresponding to the general formula in whichB represents the radicals HO, R -,-O-,

R R R o I 03 Gil-0%!!- ig 1 o" v 9 u Q or H O-CH-CH O-O-R -O-O- and R, RR 3: and m are as defined above, into the corresponding alcoholates inthe presence of an inert gas and in the absence of moisture, andreacting the resulting alcoholates at temperatures of from 20to 150C,either in the melt or in an inert solvent, with a compound correspondingto the general formula (XI):

08 a a-B Ha]. R XI) in which R,, R and M are as defined above, and Halrepresents fluorine, chlorine or bromine, accompanied by the eliminationof M-Hal.

The types in which R represents NH are obtained from the correspondingnitro compounds by catalytic hydrogenation with Raney nickel.

The following are mentioned as examples of oxalkylation products for theproduction of the new anti-static agents added in accordance with theinvention:

. co ea k 9 I 1 O The following are examples of activated halogen showsa neutral reaction. The alkali metal halide compounds for thenucleophilic substitution reaction formed during the reaction is thenisolated by filtration. according to the invention: Examples of suitableinert solvents include benzene,

dioxan, dimethyl formamide, dimethyl acetamide or 5 N-methylpyrrolidone. Nitrogen, hydrogen or helium 3 F 2 can be used as the inertgas.

. The following are mentioned as examples of the antistatic additivesaccording to the invention: R0 3 3 c1 0 cn -(cri )o{m -cn so m Q M.- 180 8a. p

$0 1k 80 Na 0 89. C1 80 C1 Q ll cB H -O 0H -0H N0 1e 35 The anti-staticagents can be prepared for example as 01 c1 follows:

For conversion into the alcoholate, the corresponding oxalkylationproduct is either reacted in the melt CHZ-CHQ- with an equimolecularquantity of an alkali metal or has H c 2 a calculated quantity of thealcoholate of a low-boiling 1'9 9 c1 c1 alcohol, for example methanol orethanol, added to it M Na 5 3N8.

3 o n-(o-cn -cngoen on -cn n0 in the absence of moisture and in an inertgas atmosphere, followed by removal of the methanol or ethanol bydistillation under reduced pressure. The alcoholate 2 N0 is then reactedeither in the melt or in an inert solvent 65 with the activated aromatichalogen compoundat tem- L10 8 o-cfl -cflgq) 30 Li peratures of from 20to C. In most cases, the reac- 3 no 3 tion is exothermic so that it isadvisible to cool the reaction mixture. The reaction is over when themixture so Na The anti-static compounds according to the invention arecompatible with solutions of acrylonitrile polymers, i.e. do not showany disintegration phenomena. Stabilisers, fillers, dyes, pigments,anti-oxidants or the like can also be added without causingdisintegration or reduction of the anti-electrostatic effect. Themixtures can readily be processed into filaments or films.

In addition to pure polyacrylonitrile, acrylonitrile polymers suitablefor the purposes of the invention include those which contain at least60 percent by weight of polymerised acrylonitrile and less than 40percent by weight of other copolymerisable compounds from the group ofvinyl and (meth) acryl compounds in copolymerised form. The followingare mentioned as examples of copolymerisable compounds: (meth) acrylicacid esters, (meth) acrylic acid amides, vinyl chloride, vinylidenechloride, and also copolymerisable compounds of the kind which bringabout an improvement in affinity for acid or basic dyes as described inUS.

.Pat. Nos. 2,649,438; 2,837,500; 2,837,501; 2,895,949

and 2,687,938.

Suitable solvents for the polymers include any of the solvents which canbe used for polyacrylonitrile, especially dimethyl formamide.

It is considerably advantageous that fibres containing the anti-staticagents according to the invention do not undergo any appreciable changesin their surface resistance, even after repeated washing with alkalinewashing agents.

In addition to their outstanding anti-static effect, the acrylonitrilepolymers according to the invention are distinguished by their highaffinity for basic dyes and by their considerably improved waterabsorption.

- In the following production specifications and Examples, parts byweight are to parts by volume as kilograms to litres.

Production of the anti-static additives A. 5.4 parts by weight of sodiummethylate are added to 121.4 parts by weight of an anhydrous ethoxylated stearyl alcohol (average molecular weight Mn 1214, determinedfrom the OH-number) in 150 parts by volume of absolute methanol.Following removal of the methanol in a water jet pump vacuum at 70C, themixture is cooled to room temperature. 26.0 parts by weight of sodium3-nitro-4-chloro-(1 )-benzene sulphonate are then introduced in portionsinto the melt while dry nitrogen is passed over. The temperature is keptat 65C by cooling. On completion of the reaction (a sample of thereaction mixture diluted with water gives a pH value of 7) the reactionmixture is dissolved in 144 parts by weight of anhydrous 'dimethylformamide containing some active carbon and separated from the sodiumchloride by filtration. Following removal of the solvent, a yellowcoloured product, wax-like at room temperature, is obtained in aquantitative yield. It has the following constitution:

ca maw-m cn 1 1 7 B. 4.6 parts by weight of metallic sodium aredissolved in 208 parts by weight of an oxethylated isononylphenol(average molecular weight IVIn 1040, determined from the OI-I-number) at120C while dry nitrogen is passed over. The alcoholate is thendissolved. in 253 parts by weight of anhydrous dimethyl formamide,followed by the addition in portions at room temperature of 51.9 partsby weight of sodium 3-nitro-4-chloro-(l)-benzene sulphonate while drynitrogen is passed over. The temperature is kept at C by cooling. Oncompletion of the reaction (neutral reaction of the reaction mixture),the mixture is isolated from the sodium chloride by filtration and thesolution hydrogenated in an autoclave with 40 parts by weight of Raneynickel at a temperature of C and under a hydrogen pressure of 63 atms.Removal of the Raney nickel and the solvent leaves 245 parts by weightof a substantially colourless product, liquid at room temperature, withthe following constitution:

i C. 4.6 parts by weight of sodium are added to 206 parts by weight ofanhydrous ethoxylated N- methylstearylamine (average molecular weight MnSO Na 1030, determined from the OH-number) while dry nitrogen is passedover, followed by stirring at l 10C until a solution is obtained.Following dissolution of the alcoholate in 300 parts by weight of drydimethyl formamide, 51.9 parts by weight of sodium 3-nitro-6-chloro-(l)-benzene sulphonate are added in portions in such a way that thetemperature does not exceed 65C. When the reaction mixture shows aneutral reaction, the mixture is filtered off from the sodium chlorideprecipitated and the solvent removed in vacuo, leaving behind, in aquantitative yield, a yellow coloured product, liquid at roomtemperature, with the following compos1tion:

D. 212 parts by weight of a segment polyaddition product with an averagemolecular weight of Mn 1060, obtained by reacting propylene oxide with apolyethylene glycol (17in 480), are reacted with 9.2 parts by weight ofsodium in 500 parts by volume of absolute dioxan at reflux temperaturewhile nitrogen is passed over. After the evolution of hydrogen hasstopped, 103.8 parts by weight of sodium 3-nitro-6- chloro-( l )-benzenesulphonate are added in portions at 70C. After 5 hours, the reactionmixture shows a neutral reaction. The reaction mixture is then filteredoff from the sodium chloride formed and the dioxan distilled off invacuo, leaving behind in a quantitative yield a pale brown colouredwax-like substance of the following composition.

SO Na E. 10.8 parts by weight of sodium methylate are added to 150 partsby weight of anhydrous ethoxylatecl isononylphenol (average molecularweight Mn 750, determined from the Ol-l-number) in 50 parts by volume ofmethanol. Following removal of the methanol in vacuo, 98.2 parts byweight of disodium 4,4- dichlorodiphenyl sulphone-( 3,3 )-sulphonate areintroduced in portions into the melt with cooling at 65 to 70C whilenitrogen is passed over. On completion of the reaction, the reactionmixture is dissolved in 400 parts by volume of dimethyl formamide,filtered off from the sodium chloride and the solvent removed by vacuumdistillation, leaving behind in a quantitative yield a pale yellowcoloured product, liquid at room temperature, with the followingcomposition:

The following Examples are to further illustrate the invention withoutlimiting it.

EXAMPLE 1 The anti-static agents described in A-E are added in differentquantities to a 27 percent dimethyl formamide solution of apolyacrylonitrile polymer (K-value according to Fikentscher of 94 partsby weight of acrylonitrile, 5 parts by weight of acrylic acid methylester and 1 part by weight of the sodium salt of methallyl sulphonicacid. The solutions are spun in a known manner by the dry-spinningprocess. After conditioning at 23C/50 percent relative humidity, thesurface resistance of the stretched filaments is measured. After theinitial surface resistance has been determined, the filaments are washedat 40C with a 0.5 percent solution of a standard detergent. Thefilaments are dried and reconditioned before the subsequent measurement.

The results are set out in Table l below and compared with those offilaments of the aforementioned copolymer without any anti-staticadditions.

ln-the same way as described in Example 1, the antistatic agentsdescribed in A-E are added in different quantities to a 27 percentdimethyl formamide solution of a polyacrylonitrile copolymer (K-value80) of 61.3 parts by weight of acrylonitrile, 37 parts by weight ofvinylidene chloride and 1.7 parts by weight of the sodium salt ofmethallyl sulphonic acid. As in Example 1, the solutions are spun intofilaments, the surface resistance of the filaments determined and thefilaments washed. The results obtained are set out in Table 2:

Table 2 R R l l (11) Anti-static Surface resistance at 23"( 50% -S02O-CH-CH A 7 addition relative humidity [(2] after after after 5 Eslrctchwashes washes ing S0 M 1 I I III III 2; y weight 10 in which R, Mand m are defined as above; and

of A 7-10 940'" no" A is 8 71 by weight IO 01' a 910'" a-m'" 9-10 10 n hll nip 2 10'" 410'" (no O X '71 by weight m D 910'" H0" H0" R O -N- IR3-c.-O.. ll) by weight H m m oih 2-10 4-10 510 (III) (IV) (v) (VI) R M0s f R 7 I1 O-CH-CH 0R -0-,

in 1 2 n MO s R1 M0 5 R1 3 R n a n R 0 o I I l I II II R -CH-CH N- or RO-CH-CH U-C-R -C-O- a a 1 2 1 R We claim: in which R, R R M and m aredefined as above; 1. A polymer composition comprising an acryloniandtrile polymer and as an antistatic agent therefor for 1 R is an alkylradical with 1 to carbon atoms, an

solids Content 0f at 40 aryl, alkylaryl or arylalkyl radical;

R is an alkylene radical with 1 to 30 carbon atoms or an aryleneradical; and

n is the number I or 2.

2. The composition of claim 1 in which said acryloni- S0 M R n 3 l5trile polymer comprises at least percent by weight I l of acrylonitrileand up to 40 percent by weight of at A 2 least one vinyl compound whichis copolymerizable E with acrylonitrile.

1 3. The composition of claim 2 in which said vinyl 2 so compoundcopolymerizable with acrylonitrile is an acrylic acid ester, an acrylicacid amide, a methacrylic in which acid ester, a methacrylic acid amide,vinyl chloride, vim is an integer f f om 1 m nyhdene Chl0l'ld 0'l amixture thereof. M is an alkali metal, an ammonium radical, or an al- 554. The composition of claim 1 in which said antikylammonium di l; staticagent has the formula to 20 percent by weight of the total least onecompound having the formula 5. The composition of claim 1 in the form ofa film.

R is a h dro en or methyl; I I R, is hyd roge n, lower alkyl radicalwith l to 6 carbon 6; 6. The composition of claim 1 in the form of afilaatoms, fluorine, chlorine. bromine or iodine; ment. R is hydrogen. z2 C1 or

1. A POLYMER COMPOSITION COMPRISING AN ACRYLONITRILE POLYMER AND AS ANANTISTATIC AGENT THEREFOR FOR 1 TO 20 PERCENT BY WEIGHT OF THE TOTALSOLIDS CONTENT OF AT LEAST ONE COMPOUND HAVING THE FORMULA((2,4-DI(R2-),DI(R1-),(M-O3S-)PHENYL)IN WHICH M IS AN INTEGER OF FROM 1TO 150; M IS AN ALKALI METAL, AN AMMONIUM RADICAL, OR AN ALKYLAMMONIUMRADICAL; R IS A HYDROGEN OR METHYL; R1 IS HYDROGEN, LOWER ARKYL RADICALWITH 1 TO 6 CARBON ATOMS, FLUORINE, CHLORINE, BROMINE OR IODINE; R2 ISHYDROGEN, -NH2, -NO2, -CN, -CF3, -CL OR(4-(A-(CH(-R)-CH(-R)-O)M-),(M-O3S-)PHENYL)-SO2IN WHICH R, M AND M AREDEFINED AS ABOVE; AND A IS R3-O-, R3-N(-R3)-, -N(-R3)-, R3-COO-,(O-CH(-R)-CH(-R))M-)N-A (2,4-DI(R2-),DI(R1-),(M-O3S-)PHENYL)-O-,(2,4-DI(R2-),DI(R1-),(M-O3S-)PHENYL)(O-CH(-R)-CH(-R))M-O-R4-O-,(2,4-DI(R2-),DI(R1-),(M-O3S-)PHENYL)(O-CH(-R)-CH(-R))M-N(-R3)-, OR(2,4-DI(R2-),DI(R1-),(M-O3S-)PHENYL)(O-CH(-R)-CH(-R))M-OOC-R4-COO-, INWHICH R, R1, R2, M AND M ARE DEFINED AS ABOVE; AND R3 IS AN ALKYLRADICAL WITH 1 TO 30 CARBON ATOMS, AN ARYL, ALKYLARYL OR ARYLALKYLRADICAL; R4 IS AN ALKYLENE RADICAL WITH 1 TO 30 CARBON ATOMS OR ANARYLENE RADICAL; AND N IS THE NUMBER 1 OR
 2. 2. The composition of claim1 in which said acrylonitrile polymer comprises at least 60 percent byweight of acrylonitrile and up to 40 percent by weight of at least onevinyl compound which is copolymerizable with acrylonitrile.
 3. Thecomposition of claim 2 in which said vinyl compound copolymerizable withacrylonitrile is an acrylic acid ester, an acrylic acid amide, amethacrylic acid ester, a methacrylic acid amide, vinyl chloride,vinylidene chloride or a mixture thereof.
 4. The composition of claim 1in which said anti-static agent has the formula
 5. The composition ofclaim 1 in the form of a film.
 6. The composition of claim 1 in the formof a filament.